Process for breaking petroleum emulsions



Patented July 18, 1944 STATES PATENT orica PROCESS FOR BRE EMUL AKIN GPETROLEUM SIONS v Melvin De Groote, University City, and BernhardKeiser, Webster Groves, Mo., 'assignors to Petrolite Corporation, Ltd.,Wilmington, Del.,'

a corporation of Delaware No Drawing. Application June 15, 1942,

Serial No. 447,163

8 Claims. (01. 252-341)' This invention relates primarily to theresolution of petroleum emulsions.

The main object of our invention is to provide a novel process forresolving petroleum emulsions of the water-in-oil type, that arecommonly referred to as cut oil," roily oil, "emulsified oil,"

etc., and which comprise fine droplets of naturally-occurring. waters orbrines dispersed in a more or less permanent state throughout the oilwhich constitutes the continuous phase of .the

emulsion.

Another object isto provide an economical and rapid process forseparating emulsions which have been prepared under controlledconditions from mineral oil, such as crude petroleum and relatively softwaters or weak brines.

under the conditions just mentioned is of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

We have discovered that if one oxyalkylates demulsification of crudeoil.

The compounds herein contemplated may be produced-in any suitablemanner, but are usually manufactured by following one of two generalprocedures. ,In oneof said procedures the oxyalkylated glycerol, whichis, in essence, a polyhydric alcohol, is reacted with a polybasic acidso as to give an acidic material, or intermediate product, which, inturn, is reacted with an alcoholic body of the kind hereinafterdescribed, and momentarily indicated by the formula R1(OH) m.Generically, the alcoholic body herein contemplated may be considered amember of the class in which m may vary from 1 to 10, although thespecific significance of m in the present instance will be hereinafterindicated. The second procedure is to react an alcohol of the formulaRl(oH)m with a polybasic acid so as to produce Controlled emulsificationand subsequent demulsification -i ll an intermediate product, and thenreact said intermediat product or fractional ester with the selectedaxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

/0H CaH5 OH OK If treated with an oxyalkylating agent, and mementarilyconsideration will be limited to an oxy ethylating agent, one may obtainan oxyethylate l glycerol of the following formula type:

(C:HAO)1UH C3H5 3-( 2 l )n'H (ClHO) UH in which the value of n may varyfrom 3 to 10 and all the values of 11' need not be identical. If

a polybasic carboxy acid be indicated by the formula:

coon

n-coon coon then the acyclic reaction product of one mole ofoxyethylated glycerol and one mole of a polybasic carboxy acid may beindicated by the following formula:

in which n" has the value of one or two. Similarly, if two moles of thepolybasic acid be used, then the compound may be indicated by thefollowing formula:

(CzHAO) '0 0 CR(C O OH) CsHsOr-(CzHACDmO O CR(C 0 0H) n" (CiHAO) n'HLikewise, if three moles of a polybasic acid are employed, the compoundmay be indicated by the following formula:

the three preceding formulas is reacted with one or more moles of analcohol of the kind previously described in/a generic sense as R1(OH) m,then obviously, one may obtaina material of the type indicated by thefollowing formula:

inwhichxis0,1or2,11is0,1or2,andzis1,2

an ammonium radical, or substituted ammonium radical, or by an organicgroup derived from an alcohol, such as an aliphatic alcohol, an aralkylalcohol, or an alicyclic alcohol. It may also be converted into anamide, includinga polyaminoamide. Thus, the preceding formula may berewritten in its broader scope, as follows:

cmtot-ucmaowm.

in which nreplaces the numbers 2, 3 or 4, z includes the acidic hydrogenatom itself. In the above formula, and hereafter for convenience, R1 isintended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usualconditions, at the lowest temperatures, then the monomeric form is mostlikely.

to result.

The production of the compounds herein conthere is at least one residualcarboxyl and at least, one residual hydroxyl, one would expect thatunder suitable conditions, instead of ob-' taining the monomericcompounds indicated, one would, inreality, obtain a polymer in thesense, for example, that polyethylene glycols represent a polymer ofethylene glycol. The term "p0lymer is.frequently used to indicate thepolymerized product derived'from a monomer in which the polymer has thesame identical composition as the monomer. the present. in-

stance, however, polymerization involves the splitting and loss of waterso that the process is essentially self-esterification. Thus, strictlyspeaking, the polymeric compounds are not ab solutely-isomers of themonomeric compounds, but since, for all practical purposes,- they can'beso indicated, and since such practice is common in the arts concernedwith materials of this type, it is so adopted here. Thus, reference inthe appended claims to. P01ymers is intended to includetheself-esteriiication products of the monomeric compounds.

In view of'what has been said, and in view of the recognized hydrophileproperties of the recurring oxyalkylene linkages, particularly theoxyethylene linkage, it is apparent that-the materials hereincontemplated may vary from compounds which are clearly water-solublethrough self-emulsifying oils, to materials which are balsam-like andsub-resinous or semi-resinous in 1 nature. The compounds may vary frommonomers to polymers, in which the unitary struc-' ture appears a numberof times, for instance,

10 or 12 times. It is to be noted that true resins,

vi. e., truly insoluble materials of a hard plastic nature, are notherein included. In other words, the polymerized compounds are solubleto a fairly definite extent, for instance, at least 5% in some solvents,such as water, alcohol, benzene,

templated is the result of one or more esterification, steps. As is wellknown, esterification procedures can be carried out in various manners,but generally speaking, esterifications can be carried out at the lowestfeasible temperatures by using one or several procedures. cedure is topass an inert dried gas through the mass to be esterified, and havepresent at the same time a small amount of a catalyst, such as dried HClgas, a'dried suli'onic acid, or the like.

One pro- Another and better' procedure, in many .in-

stances, is to employ the vapors of a suitable liquid so as to removeany water formed, and condense both the vapors of the liquid employedand the water in such a manner as to trap out the water and return theliquid to thereacting vessel. This procedure is commonly employed in thearts, and for convenience, reference is made to U. S. Patent No.2,264,759, dated December 2, 1941, to Paul C. Jones. I v

Referring again to the last two formulas indicating the compounds underconsideration, it can be readily understood that such compounds. innumerous instances, have the property of polyfunctionality. In view ofthis fac w ere dichloroethyl ether, acetone, cresylic acid, acetic acid,ethyl acetate, dioxane, or the like. This is simply another way ofstating that the polymerized product contemplated must be of thesub-resinous type, which is commonly referred to as an A resin, or a Bresin, as distinguished from a C resin, which is a highly infusible,insoluble ,resin (see Ellis, Chemistry of Synthetic Resins (1935), pages862, et seq).

Reviewing the form as presented, it is obvious that one may obtaincompounds within thescope disclosed, which contain neither afreehydroxyl nor a free carboxyl group, and one may .also obtain acompound of the type in. which there is present at least one freecarboxyl, or at least, one free hydroxyl, or both. The word "polar hassometimes been used in the arts in this particular sense to indicate thepresence of atleast one free hydroxyl group, or at least, one freecarboxyl group, or both. Inthe case of the free carboxyl group, thecarboxylic hydrogen atom may, of course, be replaced by any ionizablehydrogen atom equivalent, such, for example, as a metal, an ammoniumradical, a substituted ammonium radical, etc. In the hereto appendedclaims the word "polar is used in this specific sense. v

We are aware that compounds similar to those contemplated in the presentinstance may be derived from polyhydrox'ylated compounds having morethan three hydroxyl groups. For instance, they may be derived fromacyclic dlglycerol, triglycerol, tetraglycerol, mixed. olyglycerols,mannitol, sorbitol, various hexitolsa dulcitol, pentaerythritol,sorbitan, man'nitan. -di-' ,this specific case, although attentionpentaerythrltol monoether, and other similar compounds. Such particulartypes in which higher hydroxylated materials are subjected tooxyalkylation and then employed in the same manner as oxyalkylatedlycerol, is employed in the present instance, are not contemplated in isdirected to the same.

Reference is also made to other oxyalkylated compounds which may be usedas reactants to replace oxyalkylated glycerol, or oxyalkylated ethyleneglycol, which latter reactant is described in a co-pending applicationhereinafter referred to; The reactants thus contemplated include thetype in which there is an amino or amido nitrogen atom, particularly,when present in a low molal type of compound prior to oxyalkylation,

reference being made to polyhydroxylated materials, including thosehaving two or three hydroxyl groups, as well as those having more thanthree hydroxyl groups. Forinstance, the oxyalkylated derivatives,particularly the oxyethylated derivatives of ethyldiethanolamine,bis(hydroxyinstance, involving the introduction of two alcoholicresidues, whereas, in the present instance, one, two, or three, or more,might be introduced.

As indicated previously, the polybasic acids employed are limited to thetype having not more than eight carbon atoms, for example, oxalic,malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly,one may employ acids such as fumaric, glutaconic, and various others,such as citric, malic,-tartaric, and the like. The selection of theparticular tribasic or dibasic acid employed is usually concernedlargely with the convenience of manufacture of the finished ester, andalso the price of the reactants. Generally speaking, phthalic acid oranhydride tends to produce resinous materials, and greater care must beemployed if the' ultimate or final product be of a sub-resinous type.Specifically, the preferred type of polybasic acid is such as to containsix carbon atoms or less. Generally speaking, the higher the temperatureemployed, the easier it is to obtain large yields of esterified product,although polymerization may be stimulated. Oxalic acid may becomparatively cheap, but it decomposes readily at slightly above theboiling point of water. For this reason it is more desirable to use anacid which is more resistant to pyrolysis. when a polybasic acid isavailable in the form of an anhydride, such anhydride' is apt to producethe ester with greater ease than the acid itself. For this reason,maleic .anhydride is particularly adaptable, and also, everything elseconsidered,

the cost is comparatively low on a per molar basis,

even though somewhat higher on a per' pound basis. Succinic acid or theanhydride has many attractive qualities of maleic anhydride, and this isalso true of adipic acid. For purposes of brevity, the bulk of theexamples, hereinafter illustrated, will refer to the use of maleicanhydride, although it is understood that any other suitable polybasicacid may be employed. Furthermore, reference is made to derivativesobtained by oxyethylation, although, as previously pointed out, otheroxyalkylating agents may be employed.

'As far as the range of oxyethylated glycerols employed as reactants isconcerned, it is our preference to employ those in which approximatelyto 24 oxyethylene groups have been introduced into a single glycerolmolecule. This means that approximately five to eight oxyethyleneradicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11of German Patent No. 605,973, dated November 22, 1934, to I. G.Farbenindustrie Akt. Ges.). The procedure indicated in the followingthree examples is substantially identical with' that outlined in saidaforementioned German patent.

OXYETHYLATED GLYCEROL Example 1 weight, of caustic soda solution havinga specific gravity of 1.383. The caustic soda acts as a catalyst. Theethylene oxide is added in relatively small amounts, for instance, about44 pounds at a time. The temperature employed is from 150-180 C.Generally speaking, the-gauge pressure during the operation approximates200 Similarly,

pounds at the maximum, and when reaction is complete, drops to zero, dueto complete absorption of the ethylene oxide. When all the ethyleneoxide has been absorbed and the reactants cooled, a second smallportion, for instance, 44 more pounds of ethylene oxide, are added andthe procedure repeated untilthe desired ratio of 15 pound moles ofethylene oxide to one pound mole of glycerol is obtained. Thisrepresents 660 poulnds of ethylene oxide for 92 pounds of glyceroOxrsrnruran GLYcaRor.

Example 2 The ratio of ethylene oxide is increased to 18 pound moles foreach pound mole of glycerol.

Otherwise, the same procedure is followed as in Example 1, preceding.

QXYETHYLATED GLYCEROL 1 Example 3 The same procedure is followed as inth two previous examples, except that the ratio of ethylene oxide toglycerol is increased to 21 to one.

' to 15 ratio) prepared in the manner previously described is treatedwith one pound mole of maleic anhydride and heated at approximatelythirty minutes to two hours, with constant stirring, so

as to yield a monomaleate.

OXYETHYLATED GLYCEROL MALEATE Example 2 The -same procedure is followedas in the preceding example, except that tw o moles of maleic anhydrideare employed so as to obtain the dimaleate instead of the monomaleate.

Omrnrinsn GLYCEROL Manners Example 3 The same procedure is followedas'in the two preceding examples, except that three moles of maleicanhydride are employedso as to obtain the trimaleate.

' Oxizmrrxnx-ran GLYcsnor. Manure Example 4 The same procedure isemployed as in the preceding examples, except that oxyethylated glycerol(ratio 1 to 18) is substituted'in place of oxyethylated glycerol (ratio1 to 15).

OXYETHYLATED GLYCEROL Manners Example 5 The same procedure is employedas in thepre-.

ceding examples, except that oxyethylated glycerol (ratio 1 to 21) isemployed instead of oxyethylated glycerol (ratio 1 to or (1 to 18).

Previous reference has been made to an alcoholic body which has. beendefined generically by'the formula R1(O.H)m. The sub-generic class v -ofalcoholic compounds employed as reactants in conditions. The formationof these glyoxalidine compounds, while forming no part of the presentinvention, is indicated by the following scheme:

' wherein R represents an alkyl or alkenyl group themanufacture of thepresent compounds, are oxyalkylated imidazolines substituted in2-position by a radical containing 11-22 carbon atoms selected from thegroup consisting of alicyclic hydrocarbon radicals, aliphatichydrocarbon rad-.

icals, and aliphatic hydrocarbon radicals substi-' 'oxyalkylated tutedby hydroxyl radicals; said imidazolines containing the radical:

I wherein R denotesan aliphatic'radical and n is a whole number greaterthan 2 and less than 11.

The intermediate products herein contemplated for reaction withmaterials such as ethylene glycol dihydrogen dimaleate, arecharacterized by having a five-membered heterccyclic ring with two atomsdifierent from carbon. More spe-' cifically, they maybe considered asderivatives of imidazole, frequently referred to as glyoxaline.Imidazole (glyoxaline) is indicated by the following formula:

a as 4 The imidazolines or glyoxalidines may be considered asdihydro-derivatives of imidazole (glyoxaline); and thus the expressionsdihydroglyoxalines and glyoxalidines are often employed.

The introduction of two hydrogen ,atoms at the 4-5 position results inthe conversion of'imidazoie into dihydroglyoxaline, which may beindicated by the following formula:

As to the manufacture of imidasolines, refer ence is made to thefollowing patents: U. 8. Patents Nos. 2,215,861, 2,215,862, 2,21 5,863,and 2,215,864, dated September 24, 1940, to Waldmann and Chwala.

Imidazolines or glyoxalidines may be regarded they may be obtained byreacting polyamines be included in the broad containing from 10 to 20carbon atoms (the residue of a higher fatty acid);"Ri representshydrogen or a lower alkyl group; R2. represents an alkylene group, or alower alkyl substituted alkylene group;.and X represents a hydroxylgroup, an amino group, or an amino-alkylene substitutedamino group. SeeU." 8. Patent No. 2,214,152, dated September 10, 1940, to Wilkes.

See also U. S. Patents Nos. 2,155,877 and 2,155,878, both dated April25, 1939, to Waldmann' and Chwala.

Tlfe expression higher molecular weight carboxy acids is-an expressionfrequently employed torefer to certain organic acids, particularlymonocarboxy acids, having more than six carbon atoms, and generally,less than 40 carbon atoms. The commonest examples include thedetergentforming acids, i. e., those acids which combine with alkaliesto produce soap or soap-like bod, ies. clude naturally-occurring fattyacids, resin acids, such as abietic acid, naturally-occurring petroleumacids, such as naphthenic' acids, and carboxy' acids produced by theoxidation of,petroleum.

As will be subsequently indicated, there are other acids which havesomewhat similar characteristics and are derived from somewhatdifierentsources, and are diiferent in structure, but can indicated.

Amongsources of such acids may be mentioned straight chain and'branchedchain, saturated and unsaturated, carboxylic, aliphatic, alicyclic,fatty, aromatic, hydroaromatic, and 81'- alkyl acids including caprylicacid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacicacid, erucic acid, saturated and unsaturated higher molecular weightaliphatic acids, such as the higherfatty acids containing at least eightas dehydration products of certain amides; and

and the higher carboxylic acidsunder certain sources, for example, lard,cocoanut oil, rapeseedoil, sesame oil, palm'kernel oil, palm oil, oliveoil,'corn oil, cottonseed '.oil,sardine oil, tallow,

soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oiland other fish oil's, teaseed oil, par- The detergent-forming acids, iningeneric term previously tially or completely hydrogenated animal andvegetable oils, such as these mentioned; hydroxy and alpha-hydroxyhigher carboxylic, aliphatic and fatty acids, such as hydroxystearicacid,.dihydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenicacid, alphahydroxy capric acid, alphahydroxystearic acid, alphahydroxypalmitic acid, alphahydroxy lauric acid, alphahydroxy myristic acid,alphahydroxy cocoanut oil mixed fatty acids, alpha hydroxy margaricacid, alphahydroxy arachidic acid, and the'like; fatty and similar acidsderived from various waxes, such as beeswax, spermaceti, montan wax,Japan wax, coccerin, and carnauba wax. Such acids include carnaubicacid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid,etc. As suggested, one may also employ higher molecular weightcarboxylic acids derived, by oxidation and other methods, from paraffinwax, petroleum and similar hydrocarbons; resinic and liydroaromaticacids, such as hexahydrobenzoic acid, hydrogenated naphthoic,hydrogenated carboxy-diphenyl, naphthenic, and abietic acid; aralkyl andaromatic acids, such as hexahydrobenzoic end, hydrogenated naphthoic,hydrogenated polycarboxy-diphenyl, naphthenic, and abietic acid; aralkyland aromatic acids, such as benzoic acid, Twitchell. fatty acids,naphthoic acid, carboxydiphenyl, pyridine carboxylic acid,hydroxybenzoic acid, and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid,campholic acid, fencholic acid, cetyloxybutyric acid, cetyloxyaceticacid, chlorstearic acid, etc.

Another source of suitable acids are those commonly referred to as lacacids, such, for. example, as the acids derived from shellac. Such acidsinclude various polyhydroxy acids, for example, aleuritic acid, shelloicacid, and kerrolic acid.

As is well known, one may use substituted acids in which some othernon-functional constituent enters the structure of the fatty acid. Forinstance, one may use aryl-, hydroxy-, alkoxy-, chloro-, keto-, andamino-derivatives. Generally speaking, however, it is always preferableto use the unsubstituted acid, particularly free from substituents whichcontain either oxygen or nitrogen atoms. Generally speaking, theintroduction of hydrocarbon radicals, regardless of source, .has littleeffect, except in altering the hydrophile-hydrophobe balance.

One may also employ the blown or oxidized acids, such as blownricinoleic acid, blown oleic, etc., or estolides derived from blownoils, such as blown castor oil, blown soyabean oil, etc.

Needles to say, the acids themselves need not be employed; but one mayreadily employ any functional equivalent, such as the anhydrides, theacyl chloride, or the like. In some instances, the esters, especially inpresence of a trace or a si nificant amount of water, act as the aciditself, in that the acid is liberated. Unless specific reference is madeto a particular isomer, one may employ any isomer or mixture of variousisomers, if the acid or acids are so available. We have produceddemulsifiers, for use in our process, by the following procedures:

HYDROXYLATED INTERMEDI TE Example 1 l-aminoethyl-2-heptadecenylglyoxalidine is prepared by mixing one gram mole (282 grams) of oleicacid with. two gram moles (206 grams) of diethylene triamine, andheating the mixture for a period of about 16 hours under a distillingcolumn. Water was continuously removed until a temperature of about 245C. was reached. The quantity of water thus removed amounted to about 1.7moles. Unreacted dlethylene triamine was distilled from the reactionmixture under vacuum, and the residue then was purified by distillationat an absolute pressure of 1 mm. of mercury, at which point it boiledwithin a temperature range of 225 to 250 C. About 220 grams of the1-aminoethyl-2-heptadecyl gloxalidine was obtained as a pale yellowliquid. The product also may be designated, by reference to thereactants used in its preparation, as oleyl diethylene triamine.

Ethylene oxide is introduced into the above base at a temperature ofabout -140" 0., until the increase in weight amounts to about 2 /2 poundmoles of ethylene oxide calculated upon one pound mole of the base.

HYDROXYLATED INTERMEDIATE Example 2 The base used in the precedingexample is replaced by l-(aminoethyl ethylamino)-2-heptadecenylglyoxalidine. This glyoxalidine was prepared by reacting 1 gram mole ofoleic acid with three gram moles (438 grams) of triethylene tetramine ina vessel equipped with a distilling column. The mixture was heated for aperiod of about six hours, and water was continuously removed until atemperature of about 300 C. was reached. Approximately 1.9 moles ofwater were thus removed. The reaction mixture was then distilled undervacuum to remove excess triethylene tetramine.

HYDRoxYLATED INTERMEDIATE Example 3 Tetraethylenepentamine issubstituted for triethylene tetramine as a reactant in the precedingexample. The glyoxalidine obtained was treated as before with ethyleneoxide.

HYDROXYLATED INTERMEDIATE Example 4 Laurie acid is substituted as areactant for oleic acid in the three preceding examples.

HYDROXYLATED INTERMEDIATE Example 5 Ricinoleic acid is substituted foroleic acid in Examples 1-3, preceding.

HYDROXYLATED INTERMEDIATE Example 6 .Naphthenic acid is substituted foroleic acid in Examples 1-3, preceding.

HYDROXYLATED INTERMEDIATE Example 7 An equivalent molal amountof'propylene oxide is substituted for ethylene oxide in Examples 1-6,

preceding.

The preferred type of demulsifier is obtained by the action of 2-10moles 0f the oxyalkylating agent, for instance, ethylene oxide orpropylene oxide, on one mole of the imidazoline.

In the hereto appended claims, the addition products formed by reactionwith acids or the basic form by reaction with water, is includedwithinthe sco e of the claims. Similarly, where the claims specify thepresence'of the group:

. N(RO)aH; NH(R'O)eH i. e the group introduced by oxyalkylation attheamino hydrogen position, "-it is understood"=that R includes groupsderived from glycid or the like. Specific attention is directed to thefact that one may use various oxyalkylating agents in addition to thosealready indicated. For instance, note the oxyalkylating agentsspecifically enumerated in the aforementioned U.' S. Patent No.2,211,001, and also in U. S. Patent No. 2,208,581,

dated July 23, 1940, to Hoeflelmann. All the oxyalkylatingagentsmentioned in both of the previously designated patents maybeemployed as reactants for the manufacture of demulsifying agentscontemplated in the present process.

COMPLETED Monousnrc DERIVATIVE Example 1 One pound mole of a product ofthe kind deunder the heading Oxyethylated glycerol maleate, Example 1 isreacted with one pound mole of Hydroxylated intermediate, Ex-

adds three pound moles of (Hydroxylated intermediate, Example 1) forreaction.

COMPLETED MonouERIc DERIVATIVE Example 6 Reference to the precedingexamples will show that in each and every instance oxyethylated glycerol(ratio 1 to 15) has been employed as a raw material or primaryreactant.- In the present instance, a more highly oxyethylated glycerolis employed, to wit, one involving the ratio of 1 to 18. (SeeOxyethylated glycerol maleate, Example 4, preceding.)

Qom'LETEn MONOMERIC DERIVATIVE Example 7 The same procedure is followedas in Example 6, immediately preceding, except that the'oxyample 1-preferably in the absenceof any high boiling hydrocarbonor inertsolvent. However,

if an inert vaporizing solvent is employed, it is generally necessary touse one which has a higher boiling range than xylene; and sometimesremovalof such solvent might present a difliculty. In other instances,however, such high boiling inert-vaporizing solvent, if employed, mightbe permitted to remain in the reacted mass and appear as a constituentor ingredient of the final product. In any event, our preference is tocon duct the reaction in the absence of any such solvent and permit thereaction to proceed with-the elimination of water. .The temperature ofreaction is about 180-to 200 C. and time of reaction about 20 hours.-

' COMPLETED MonouERIc DERIVATIVE I Example 2 The same procedure isfollowed as in Completed monomeric derivative, Example 1, preceding, ex-

cept that the dimaleate described under the heading Oxyethylatedglycerol maleate, Example 2 is used instead of the monomaleate.

comma-an Monomnuo DERIVATIVE Example 3 The same procedure is followed asin the two preceding examples, except that the trimaleate is substitutedfor the monomaleate or dimaleate in the two preceding examples.

COMPLETED MoNonERIc DERIVAT E Example 4 I The same procedure is followedas in Examples 2 and 3, immediately preceding, except that for eachpound mole of the maleate, or each pound mole of the trimaleate, insteadof using one pound mole of (Hydroxylated intermediate, Example 1) as areactant, oneemploys two pound moles.

OMPI-ETED Monousnrc DERIVATIVE Example 5 The same procedure is followedas in Example 3, preceding, except'that for each poundmole oftrimaleate, instead of adding one pound mole of (Hydroxylatedintermediate, Example 1) one ethylated glycerol employed represents onehaving an even higher degree of oxyethylation. For example, oneindicated by the ratio of 1' to 21. (See Oxyethylated preceding.) r

' COMPLETED MONOMERIC DERIVATIVE Example 8 The same procedure isfollowed as in Examples 1 to 7, preceding, except that instead ofemploying Hydroxylated intermediate, Example 1, preceding, one employsinstead Hydroxylated intermediate, Example 2, preceding. I COMPLET DMONOMERIC DERIV TIVE Example 9 The same procedure is followed as inExamples 1 to 7, preceding, except that instead of employingHydroxylated intermediate, Example 1, one employs instead Hydroxylatedintermediate, Ex-

ample 3.

Com'LETEn MONOMERIC DERIVATIVE Example 10 The same procedure is followedas in Examples 1 to 7, preceding, exceptthat instead of employingHydroxylated intermediate, Example 1, one' employs instead Hydroxylatedintermediate, Example 4.

The method'of producing such fractional esters is well'known'. Thegeneral procedure is to employ a temperature above the boiling point ofwater and below the pyrolytic point of the reactants. The products aremixed and stirred 0011-.

stantly during the heating and esterification step. I If desired, aninert gas, such as dried nitrogen or such water of esterification isabsent when such type of reaction involves an'acid anhydride, such asmaleic anhydride, and a glycol. However, if

water is formed, for instance,.when citric acid is employed, then asolvent such as xylene may be present and employed to carry off thewater formed. The mixture of xylene Vapors and water Vapor's can becondensed so that the water is glycerol maleate, Example 5,.

separated. The xylene is then returned to thereaction vessel for furthercirculation. This is a conventional and well-knownprocedure and requiresno further elaboration.

In the previous monomeric examples there is a definite tendency, inspite of precautions, at least in a number of instances, to obtainpolymeric materials and certain 'cogeneric by-products. This is typical,of course, of organic reactions of this kind, and as is well known,organic reactions per se are characterized by the fact that 100% yieldsare'the exception, rather than the rule, and that significant yields aresatisfactory, especially in those instances where the by-products orcogeners may satisfactorily serve with the same purpose as the principalor intentional product. This is true in the present instance. In manycases when the compound is manufactured for purposes of demulsification,one is better off to obtain a polymer in the sense previously described,particularly a polymer whose molecular weight is a rather small multipleof the molecular weight of the monomer, for instance, a polymer whose.

molecular weight is. two, three, four, five, or six times the molecularweight of the monomer. Polymerization is hastened by the presence of analkali, and thus, in instances where it is necessary to have a maximumyield of the monomer, it may be necessary to take such precautions thatthe alkali used in promoting oxyethylation of glycerol, be removedbefore subsequent reaction. This, of course, can be done in any simplemanner by conversion to sodium chloride, sodium sulfate, or any suitableprocedure.

-In the preceding examples of the Completed monomeric derivative,Examples 1 to 10, inclusive, no reference is made to the elimination ofsuch alkaline catalyst, in view of the effectiveness of the ,lowmultiple polymers as demulsifiers. Previous reference has been made tothe fact that the carboxylic hydrogen atom might be variously replacedby substituents, including organic radicals, for instance, the radicalsobtained from alcohols, hydroxylated amines, non-hydroxylated amines.polyhydric alcohols, etc. Obviously, the reverse is also true, in that afree hydroxyl group may be esterified with a selected acid, varyingfromsuch materials as ricinoleic acid to oleic acid, including alcoholacids, such as hydroxyacetic acid,

lactic acid, riclnoleic acid and also polybasic acids of the kind hereincontemplated.

With the above facts in mind, it becomes obvious that what has beenpreviously said as to polymerization, with the suggestion thatby-products or cogeneric materials were formed. may be recapitulatedwith greater definiteness, and one can readily appreciate that theformation of heatrearranged derivatives or compounds must take plac to agreater or lesser degree. Thus, the products herein contemplated may becharacterized by being monomers of the type previously described, oresterification'polymers, or the heatrearranged derivatives of the same,and thus including the heat-rearranged derivatives of both the polymersand esteriflcation monomers, separately and jointly. Although the classof materials specifically contemplated in this instance is acomparatively small and narrow class of a broad genus, yet it isobviously impossible to present any adequate formula which wouldcontemplate the present series in their complete ramification, except ina manner employed'in the hereto appended claims.

- Although the products herein contemplated vary so broadly in theircharacteristics, i. e.,

monomers through sub-resinous polymers, soluble products,water-emulsifiable oils or compounds, hydrotropic materials, balsams,sub-resinous materials, semi-resinous materials, and the like, yet thereis always present the characteristic unitary hydrophile structurerelated back to the oxyalkylation, particularly the oxyethylation of theglycerol used as the raw material. As hereinafter indicated, in theresolution of oil field emulsions, the demulsifier may be added to theemulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in30,000, or for that matter, 1 part in 40,000. In such ratios it well maybe that one can not differentiate between the solubility of a compoundcompleted soluble in water in any ratio, and a semi-resinous productapparently insoluble in water in ratios by which ordinary insolublematerials are characterized. However, at such ratios the importance mustreside in interfacial position and the ability to usurp, preempt, orreplace the interfacial position previously occupied perhaps by theemulsifying colloid. In any event, reviewed in this light, the obviouscommon property running through the entire series, notwithstandingvariation in molecular size and physical make-up, is absolutelyapparent. Such statement is an obvious over-simplification of therationale underlying demulsification, and does not even consider theresistance of an interfacial film to crumbling, displacement, beingforced into solution, altered wetability, and the like. .As toamidification polymers, forinstance, where Z is a polyaminoamideradical, see what is said subsequently.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERSExample 1 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGEDCOGENERS Ezrample 2 The same procedure is followed as in the precedingexample, except that polymerization is continued, using either asomewhat longer reaction time, or it may be, a somewhat highertemperature, or both, so as to obtain a material having a molecularweight of approximately three to four times that of the initial product.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERSExample 3 The same procedure is followed as in Example, 1 and 2,preceding, except that one employs as a reactant a material of the kinddescribed under the heading "Hydroxylated intermediate, Example 2,instead of -Hydroxy1ated intermediate, Example 1, as in the previousexamples.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERSExample 4 The same procedure is followedas in Examples 1 to 3,preceding, except that one polymerizes a mixture instead of a singlemonomer, for instance, a mixture of materials of the kind described inCompleted monomeric derivative, Ex-

product need not be obtained as a result of a two,

step procedure. In other words, one need not convert the reactants intothe monomer and then sub sequently convert the monomer into the polymer.The reactants may be converted through the monomer to the polymer, inone step. Indeed, the

formation of the monomer and polymerization may take placesimultaneously. This is especially true if polymerization is conductedin the absence of a liquid such as xylene, as previously described, andif one uses a comparatively higher temperature, for instance,approximately 220 C. ,for polymerization. Thus, one pound mole of anoxyethylated glycerol polymaleate of the kind previously described ismixed with one pound mole of an alcoholic body of the kind'describedunder the heading Hydroxylated intermediate, Example 5." Such mixture isreacted for approximately hours at about 220 C. until the mass ishomogenous. It is stirred constantly during reaction. Polyfunctionalitymay reside indehydration (etherization) of two hydroxyl groups attachedto dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be "madein a single step, illustrates a phenomenon which sometimes occurs eitherin such instances where alcoholic bodies of the kind herein illustratedare contemplated as reactants, or where somewhat kindred alcoholicbodies are employed. The reactants may be mixed mechanically to ,give ahomogeneous mixture, or if the reactants do not mix to give ahomogeneous mixture, then early in the reaction v stage th re is formed,to a greater or lesser degree,

sufllcient mon 'nericmaterials so that a homogeneous system is present.Subsequently, as reaction continues, the system may become heterogeneousand exist in two distinct phases, one being possibly an oily body ofmoderate viscosity,

conventional demulsifying agents, provided that such compounds arecompatible. They will be compatible with the hydrophile type ofsolvent-in all instances. Moreover, said material or materials may beused alone, or in admixture with other suitable well-known classes ofdemulsifying agents.

It is well-known that conventional demulsifying agents may b used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oil and water-solubility. Sometimes they may be used in a formwhich-exhibits relatively limited oil-solubility. However, since suchreagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000,or even 1 to 30.000, such-an apparent insolubility in oil and water isnot significant, becaus said reagents undoubtedly have solubility withinthe concentration employed. This same fact is true in regard to thematerial or materials herein described, except that they are invariablywater-soluble.

We desire to point out that the superiority of the reagent ordemulsifying agent contemplated in our herein described process forbreaking petroleum emulsions, is based upon its ability to treat certainemulsions more advantageously and at a somewhat lower cost than ispossible with other available demuls'iflers, or conventional mixturesthereof. It is believed that the particular demulsifying agent ortreating agent herein described will find comparatively limited applicaton, so far as the majority of oil field emulsions are concerned; but wehave found that such a de'mulsifying agent has commercial value, as itwill economically break or resolve oil field emulsions in a number ofcases which cannot be treated as easily or at so low a cost with thedemuisifying' agents heretofore available.

In practising our improved process for resolving petroleum emulsions ofthe water-in-oil type,

a treating agent or demulsifying agent of the kind above described isbrought into contact with or caused to act upon the emulsion to betreated,

. in any of the various ways, or by any of the variand the other being aheavier material, which is st cky or sub-resinous in nature. In manyinstances it will be found that the thinner liquid' material is amonomer and the more viscous or resinous material is a polymer, as

. alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexy1alcohol, octyl alcohol, etc.,may beemployed as d luents. Miscellaneoussolvents, such as pine oil, carbon tetrachloride, sulfur dioxide extractobtained in the refining of petropreviously described. Such product canbe used for demulsiflphases and employing each ous apparatus nowgenerally used, to resolve or break petroleum emulsions with a chemical.Y reagent, the above procedure being used either alone, or incombination with other demulsifying procedure, such as the electricaldehydration process.

The demulsifier herein contemplated may be employed in connection withwhat is commonly known as down-the-hole procedure, i.e., bringing thedemulsifier in contact with the fluids of the well at the bottom of thewell, or at some point prior to their emergence. This particular type ofapplication is decidedly feasible when the demulsifier is used inconnection with acidification of calcareous oil-bearing strata,especially if 'suspended in or dissolved in the acid employed foracidification.

Cognizance must be taken of the fact that the surface of the reactingvessel may. increase or decrease reaction rate and a degree ofpolymerization, for instance, an iron reaction vessel speeds up reactionand'polymerization, compared with leum, etc., may be employed asdiluents. Similarly, the material or materials herein described, whenemployed as demulsifiers for water-in-oil emulsions, may be admixed withoneor. more of the solvents customarily used in oonnection'withaglass-lined vessel. As has been previously indicated, the sub-genusemployed as an alcohol in the present instance is one of a series ofalcoholic compounds which are contemplated in our' co-pendingapplications Serial Nos. 447,151, 447,152, 447,153, 447,154, 447,155,447,156, 447,157, 447,158, 447,159, 447,160, 447,161, 447,162, 447,164,447,165, 447,166, 447,167,

and 447,168, filed June 15, 1942.

' aliphatic hydrocarbon It is to be noted that in such instances wherethe alcoholic body contains a reactive amino hydrogen atom, forinstance, in the case where an acylated hydroxylated polyamine isemployed, for example, the ricinoleyl acid ester of hydroxyethylethylenediamine, the oxyethylated glycerol maleate might react to forman amide of maleic acid. In such instances, of course, such type, towit, the amido type, is contemplated within the scope of the appendedclaims in the particular instance, but elaboration is eliminated,because it is unnecessary and would only incur greater length ofdescriptive matter. Thus, stated in another way, in all appropriateinstances, the expression esterification polymers" in the appendedclaims, includes amidification polymers, as well as esterificationpolymers.

Having thus described our'invention, what we claim as new and desire tosecure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a member of the class consisting of monomers, sub-resinousesterification polymers, and cogeneric sub-resinous heat-rearrangedderivatives of themonomers and aforementioned polymers, separately andjointly, and of the following formulaz o o 02 cmmmowoooa in which R isthe carboxyl-free radical of a-polybasic carboxy acid having not over 8carbon atoms; R1 is an oxyalkylated imidazoline radical substituted intwo-position by the radical containing 1l22 carbon atoms selected 'fromthe class consisting of alicyclic hydrocarbon radicals,

radicals and aliphatic hydrocarbon radicals substituted by hydroxylradicals; said oxyallwlated imidazoline radical containing a groupselected from the-class consisting of -N-(R"-O)1|.H and -NH-(R"-O)1r H-groups; wherein R" denotes an aliphatic radical and n is a small wholenumber greater than 2 and 50 less than 11; Z is an acidic hydrogen atomequivalent including the acidlc hydrogen atom itself; m represents thenumerals 2 to 4; n represents the numerals 3 to 10; n" represents thenumerals 1 to 2; :1: represents the numerals 0 to 2; 11 represents thenumerals 0 tn 2; 2 represents the numerals 1 to 3; :1 represents thenumerals 0 to 1; and y represents the numerals 1 to 2.

2. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subject- 60 mg the emulsion to the action of ademulsifier comprising a member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheat-rearranged derivatives of the monomers and aforementioned epolymers, separately and jointly, and of the following iormula:

[(c..,1=n..0),.'0o0200021z CQHEO8' [(CIHQIO)D'H]I (o..,ns..o oooaooon,in which R is a carboxyl-free radical of a dibasic carboxy acid havingnot over 6 carbon atoms; R1 is an oxyalkylated imidazoline radicalsubstituted in two-position by a radical containing 11-22 car- 75 bonatoms selected from the class consisting of alicyclic hydrocarbonradicals, aliphatic hydrocarbon radicals and aliphatic hydrocarbonradicals substituted by hydroxyl radicals; said oxyalkylated imidazolineradical containing a group selected from the class consisting of groups;wherein R" denotes an aliphatic radical and n is a small whole numbergreater than 2 and less than 11; Z is an acidic hydrogen atom equivalentincluding the acidic hydrogen atom itself; m represents the numerals 2to 4; n represents the numerals 3 to 10; :n represents the numeralO to2; 11 represents the numerals 0 to 2; and z represents the numerals 1 to3.

3. A process for breaking petroleum emulsions of the waten-in-oil type,characterized by subin which R is a carboxyl-free radical of a dibasiccarboxy acid having not over 6 carbon atoms; R1 is an oxyalkylatedimidazoline radical substituted in two-position by a radical containingl1-22 carbon atoms selected from the class consisting of alicyclichydrocarbon radicals, aliphatic hydrocarbon radicals and aliphatichydrocarbon radicals substituted by hydroxyl radicals;

said oxyalkylated imidazoline radical containing a group selected fromthe class consisting of -N--(R' 'O) "H and -NH(R' 'O) nH- groups;wherein R" denotes an aliphatic radical and n is a small whole numbergreater than 2 and less than 11; Z is an acidic hydrogen atom equivalentincluding the acidic hydrogen atom itself; 11. represents the numerals 3to 10; :1: represents the numerals 0 to 2; 11 represents the numerals 0to 2; and 2 represents the numerals 1 to 3.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheat-rearranged derivatives of the monomers and aforementioned polymers,separately and jointly, and of the following formula:

in which R is a carboxylfree radical of a dibasic carboxy acid havingnot over 6 carbon 5 atoms; R1 is an oxyalkylated imidazoline radicalsubstituted in two-position by a radical containing 11-22 carbon atomsselected from the class consisting of alicyclic hydrocarbon radicals,aliphatic hydrocarbon'radicals and aliphatic hydrocarbon radicalssubstituted by hydroxyl radicals; said oxyalkylated imidazoline radicalcontaining a group selected from the group consisting of groups; whereinR" denotes an aliphatic radicaland n is a small whole number greaterthan'2 a and less than 11; Z is an acidic hydrogen atom equivalentincluding the acidic hydrogen atom itself; n represents the numerals 3to 10; a: rep,- resents the numerals to 2; :11 represents the numerals 0to 2; and z represents the numerals 1 Y to '3. l l

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheatrearranged derivatives of the monomers and aforementioned polymers,separately and jointly, and of the following formula:

group selected from the class consisting of groups; wherein R" denotesan aliphatic radical and n isa small whole number greater than 2and'less than 11; Z is an acidic hydrogen atom equivalent including theacidic hydrogen atom itself; 11. represents the numerals 3 to a: rep-.resents the numerals 0 to 2; y represents the numerals 0 to 2; and zrepresents the numerals 1 to 3.

6. A process for breaking petroleum emulsions; of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidicmember of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheatrearranged derivatives of the monomers and aforementioned polymers,separately and Jointly, and of the following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid havingnot over 6 carbon atoms; R1 is an oxyalkylated imidazcline radicalsubstituted in two-position by a radical having 18 carbon atoms selectedfrom the class consisting of alicyclic hydrocarbon radicals, aliphatichydrocarbon radicals and aliphatic hydrocarbon radicals substituted byhydroxyl radicals; said oxyalkylated imidazcline radical containing agroup selected from the class consisting of -N--(R"O) "H and NH--(R''-o) "H- groups; wherein R" denotes an aliphatic radical and n is asmall wholenumber greater than 2 and less than 11; Z is an acidichydrogen atom equiv alent including the acidic hydrogen atom itself;

11' represents the numerals 3 to 10; :1: represents 5 the numerals 0 to2; y representsithe numerals O'to 2; and 2' represents the numerals 1 to3.

7. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifiercomprising a polar acidic member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheatrearranged derivatives of the monomers and aforementioned polymers,separately and jointly, and of the following formula:

in-which R is a carboxy acidhaving not over 6 carbon atoms; R1 is anoxyalkylated imidazcline radical substituted in two-positionby a higherfatty acid radical having 18 carbon atoms; said oxyalkylated imidazcineradical containing a group selected from the class consisting of groups;wherein R" denotes an aliphatic radical and n is a small whole numbergreater than 2 and less than 11; Z is an acidic hydrogen atom equivalentincluding the acidic hydrogen atom itself;

n represents the numerals 3 to 10; a: representsv the numerals 0 to 2;11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

8. A process-for breaking petroleum emulsions of the water-in-oil type,characterized by sub- .jecting the emulsion to theaction of ademulsifier comprising a polar acidic member of the class consisting ofmonomers, sub-resinous esterification polymers, and cogenericsub-resinous heatrearranged derivatives of the monomers andaforementioned polymers, separately and jointly, and of the followingformula:

groups; wherein R" denotes an aliphatic radical and n is a small wholenumber greater than 2 and less than 11'; Z is an acidic hydrogen atomequivalent including the acidic hydrogen atom itself; n represents thenumerals 3 to 10; .1: represents the numerals 0 to 2; 11 represents thenumerals 0 g to 2; and 2 represents the numerals 1 to 3.

NIELVIN DE GROOTE. B KEISER.

carboxyl-free radical of a dibasic I

